Synthetic lubricants by the catalytic treatment of unsaturated ketones



Patented July 12, 1949 UNITED STATES PATENT ()FFICE SYNTHETIC LUBRICANTS BY THE CATA- LYTIC TREATMENT OF KETON ES UNSATURATED Ferdinand P. Otto, Woodbury, N. J assignor to Socony-Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Application January 23, 1947, Serial No. 723,890

2 Claims.

treatment with reduced iron powder or red iron oxide at around 650 F. under a positive pressure of 20 to 40 pounds per square inch, in accordance with United states patent application Serial No. 490,682, filed June 12, 1943, by Meyer and Otto, on Method of preparing high molecular weight aliphatic ketones, now United States Letters Patent No. 2,410,096. Similar unsaturated ketones having to 30 carbon atoms in each alkene radical are known.

According to the present invention, it has been discovered that such compounds can be converted into new products that differ greatly in physical and chemical characteristics from the starting ketones, and that have properties that make them valuable as synthetic lubricating oils.

A number of catalysts are satisfactory for the conversion of unsaturated ketones to new products of the type with which this application is concerned. Among these are hydrogen fluoride. a pelleted synthetic silica-alumina cracking catalyst comprising about 88% S102 and 12% A120: on a dry basis, an activated montmorillonite clay marketed by the Filtrol Corporation, bead catalyst, which is a silica-alumina catalyst formed from a true hydrogel into spheres, and containing approximately 90% SiOz and 10% A1203.

By treating the unsaturated ketones mentioned above with any one of the three solid catalysts mentioned, at a temperature of about 500 to 650 F. for about 3 to 7 hours, the ketones are converted into products which compare favorably with the most highly-refined, oxidationresistant, mineral lubricating oils. These products have extremely high viscosity indices.

Analysis indicates that the percentage of oxygen in the conversion products is considerably less than is present in the starting ketones, and it is reasonable to believe therefore that water is split from the molecule, or molecules, during the reaction.

The iodine number of the products indicates that at least one double bond in the unsaturated ketone molecule is utilized in the reaction and it is reasonable to theorize that the reaction involved is therefore dependent also upon the oleflnic nature of the ketone. The necessity oi I using an unsaturated ketone is further substantiated by the fact that lfi-hentriacontanone, a saturated aliphatic ketone, failed to yield a con.- version product under similar conditions.

The molecular weights of the conversion products are on the average about the same as, or a little lower than, the starting ketone. This indicates that the reaction'involved is probably not a polymerization. It also indicates that the products obtained are derived by a single reac tion involving the double bond and carbonyl group in a single molecule of the unsaturated ketone. If an interaction occurred, involving more than one molecule of the ketone, the molecular weights of the products would be expected to be considerably higher than they have proved to be.

From these facts it can be reasoned that the 7 conversion products are probably cyclic hydrocarbons formed by a reaction of the carbonyl group with a double bond, or bonds, contained in the unsaturated ketone. A more remote mechanism might involve cracking of the oleone molecule followed by polymerization or condensa-v tion of the fragments into products of the physical and chemical properties described.

, .mm I

Pssrmrrox or Orson Oleone (di-heptadecenyl ketone) was prepared from commercial grade oleic acid. known as White Elaine red oil, in an autoclave equipped with a mechanically-driven stirrer and a pressure relief valve which was set to maintain a positive pressure of 20 to 40 pounds per square inch at all times. Into this autoclave was charged 1500 g. of the oleic acid and finely-divided reduced iron powder was then stirred into the acid.

The autoclave was closed and the mixture stirred and heated. The temperature was maintained at 625 F. for about 3 hours. Reaction was subbenzol, was then removed from the filtrate by distillation and 1200 g. of a pale yellow, wax-like material were recovered. This material had a neutralization number of 0.95, an iodine number of 100, and an aniline point of 38.4 C.

This same general procedure was used in the preparation of all of the oleone used in the following examples.

EXAMPLEII OLIONI-PILLETID Smell-Arms CATALYST Rnsc'rron Paonu'cr Oleone prepared as above was reacted in the presence of a pelleted synthetic silica-alumina cracking catalyst, comprising about 88% S10: and 12% A120: on a dry basis, by placing 2400 g. of oleone and 480 g. of the catalyst in a'l-gallon gas-fired stirring autoclave and heating to 625 F. for a period of hours. The product was diluted with about 500 cc. of A. S. T. M. precipitation naphtha and filtered through adsorptive clay. The filtrate was then topped under vacuum at 300 F. in order to remove the naphtha diluent and any low-boiling components formed during the reaction. The result was a yellow-green, fluorescent oil of which 1850 g. were recovered. This corresponds to a yield of 77% on the basis of the oleone used.

Chemical and physical properties of Product A. P. I. gravity 29.8 Kinematic visc. at 100 F 86.1 Kinematic vise. at 210 F 11.6 Viscosity index 126 A. S. '1. M. pour point, "1'' 0 Aniline point, "C 96.0 Iodine number 44 Refractive index at 20 C 1.4912

EXAMPLE III The product of Example 11 was de-waxed by treating it with 4 volumes of ade-waxing solution consisting of 40% methyl ethyl ketone, 57% benzene, and 3% toluene. The de-waxing was accomplished in the conventional manner at -20 F. and the filtrate was topped under vacuum at 820 1''. to remove the de-waxing solvent and any light ends still remaining in the com- 4 a position A small amount of a hsrd-wax-iike substance representing 2.58% or the oil charged. was removed from the composition by the dewaxing solvent. The yield of de-waxedmaterialwas80.5% ofthestartingquantity.

Physical and chemical properties of ale-waxed Product A. P. I. gravity 28.1 Kinematic visc. at 100 1" 148.7 Kinematic visc. at 210' 1" 16.24 Viscosity index 117 A.'B. T. M. pour point, P +5 Aniline point, "C 126 Iodine number 46 Refractive index at C 1.4960

Molecular weight s95 EXAMPLE! The composition of Example III was hydnogenated by placing 800 g. of it and g. of a nickel oxide hydrogenation catalyst manufactured by the Universal Oil Products Company in a 2-liter shaker bomb pressurized with hydrogen to 1675 pounds per square inch and heating to 500 F. for 3 to 6 hours. During the last hour of operation the rate of pressure drop was negligible, thereby indicating that hydrogenation was complete. The product was diluted with about 500 cc. of benzol, filtered to remove the catalyst and topped under vacuum at 175 0., to remove the solvent.

Physical and chemical properties of hydrogenated product A. P. I. gravity 29.4 Kinematic vise; at 1' 144.6 Kinematic vise. at 210! 15.85 Viscosity index 117 A. S. T. M. pour point, F 0 Aniline point, C 139 Iodine number 19 Refractive index at 20' C ...1 1.4863 Molecular weight 456 EXAMPLE V Orson-HP Paonucr Oleone was reacted in the presence of hydrogen fluoride at 70 1". by stirring a mixture of 197 g. of oleone and 102 g. of hydrogen fluoride together at 70 F. for a period of 7 hours, in a 1-liter Monel lined autoclave. The hydrogen 1 fiuoride was then released into an alkali trap and the product poured into a dilute solution of potassium hydroxide. After dilution with about 300 cc. of benzol the mixture was water washed until neutral and topped under vacuum at 300,1". The yield was 178 g. of a slightly viscous oil.

Physical and chemical pr r ies of product Following the general procedures described in the preceding examples, a series of products have entam Prepared as may be seen from the following um I [MOII'OOIIIRIOII and yield] mm: Rm Sample v 1 k No. Per cent Type Per cent 9?" &2? Pram, Olin.

None None 100 0 n (In 100. 0 25 660 5. 5 About 200 Bomb 74. 5 25 550 0.0 ---d0 --do 78.0 25 000 0.5 ......do --d0 91.5 (Produot 6 dewuxed at -23 F.. 47 solids removed) 25 575 a. o I Atmocpherim-.- Flask no 25 650 5.0 About M. Bomb 87. 0 roduet 8 hydrogenated using nickel catalyst at 500 F.

v 600 5.0 l About 110.. l Autoclave..- 86.0 (Product 10 downed at -1s F. topped at 325 It, 4. material remov 625 I 5. 0 About 200 toelsve..-| 1a. a

- (Product 12 dewexed at -20 F., topped at 32512., 11.4% material removed) (Product 13 hydrogenated using nickel catalyst at 600 F.) Si-Al 20 I 625 l 5-0 I About "I Autoc1ave.. 84.0

Y (Product 16 dewaxed at 2) F.) (Product 16 hydrogenated using nickel catalyst at 500 F.)

105 5. A at 16 70 0 b0 Autgclave... 52 70 7. 0 About 0 61 200 4. 0 t 95 310 4 0 67 450 v 2 0 050 4 5 25 575 4 5 d0 25 700 2 5 Adsorbent clay-.-- 2a 575 3 5 d0 25 575 5 0 [Properties of reaction products] Iodine Gravity Sp. Gr. Kin. Visc. Kin. Vlsc. Kin. Vise. N0. v API at 60 F. at 210 F. at 100 F. Index 92 30. 5 8735 B. 38 45. 96 147 1% 30. 8 8718 7. 71 37. 3 140 3.6 .8838 13.93 117.9 119 49 28. 4 8849 22. 26 218. 6 120 30 E. 1 8860 20. 12 197. 0 11B 27. 7 8888 21. 32 218. 1 117 19 3. 9 8882- 17. 67 110. 9 119 24 28. 5 8844 12. 52 M. 3 122 13 31. 3 8692 13. 47 110. 3 121 50 28. 7 8833 14. 88 127. 5 120 50 28. 6 8838 18. 11 167. 1 119 44 28. 9 8822 11. 70 86. 1 120 46 28. 1 8866 16. 24 148. 7 117 19 29. 4 8794 15. 85 144. 6 117 28. 4 8849 18. 59 169. 0 121 10 30. 7 8724 17. 18 153. 2 121 87 20. 7 8944 44. 96 531. 0 121 68 24. 9 .,1X)47 61. 798. 0 121 69 25. 8 8996 294. 30 4990. 0 52 23. 3 .9141 v 39. 70 62B. 0 106 20 25. 6 .9007 2). 223. 0 112 32 28. 2 8800 13. 30 111. 8 118 56 28. 5 8844 17. 44 153. 3 122 39 28. 5 8844 9. 41 67. 5 122 30 28. 2 886.0 15. 83 133. 9 122 20 28. 4 8849 14. 29 126. 4 116 [Properties of reaction products] u R z Ind P o 1: P c 1; Percent Sam lo No. Point, Am .3 M01. wc. en 0 by P 0 PL, 0. at 20 0. 0. H Difference Several practical tests 01 the new materials have been made to determine their utility as synthetic lubricants.

A rotating cylinder test was conducted in a reaction chamber consisting of a 99-inch section of standard -inch iron pipe. Each end was closed with a flat steel plate, one end being equipped with a thermometer well and a fi-inch end was used to conduct air to the bottom 0! the test tube. The test tube was placed in a constant temperature bath and held at 175 0. while air was blown through the test oil at a rate of 2 liters per hour during the test. The loss in weight in milligrams of the bearing during the test was determined and also the changes in characteristics of the oil.

The results of a series of these tests are given in the following table.

. TABLE 111. [Modified bubble tea Bearing K. V. at K. V. at Duration of K. V. at A. B. T. M. 100 F. 210 F. Test, Hours M 210 F. .Sludge i a 111. 0 13.03 110 40 0.4 1 21s. a 22.20 120 24 3. a 0 111. s 13.30 11s 48 4. s m use. 3 11.44 122 4a a. 1 a 01. a 0.41 122 4a 3. 0 10 531. 0 44.00 121 48 0.8 11

inside diameter air vent. The cylinder was rotated about a horizontal axis at R. P. M. so that the sample wetted the entire curved surface. The cylinder was enclosed in an insulated box, and electrically heated. I

cc. of the test oil was placed in the clean, sand-blasted cylinder. The vessel was started rotating with the heater adjusted to maintain the temperature in the reaction chamber at 300 F. After '12 hours the cylinder was allowed to cool to room temperature. The test oil was then removed from the apparatus and tested for kinematic viscosity at 100 F., kinematic viscosity at 210 F., neutralization number, and A. S. T. M. naphtha insolubles. The surfaces of the cylinder were examined for abnormal sludge or lacquer deposits after the completion of the test.

The following table shows the results of this test on several samples.

EXAMPLE VIE A series of Lauson piston detergency tests were also conducted on the new materials. The purpose of this test is to measure the effectiveness of the test oil in preventing piston fouling as measured by the cleanliness of rings, lands, ring grooves, skirt and inside crown of the piston. In the test, a hall-gallon of sample is used in a Lauson single-cylinder, four-cycle, liquidcooled engine with jet lubrication. The fuel used is straight-run gasoline plus 2 cubic centimeters of .tetraethyl lead, and under operating conditions the oil temperature is 225 F., the jacket temperature 350 F., speed 1830 R. P, M., the throttle setting V and the fuel-air ratio 13:1. The rating is based on engine cleanliness at the end of a run of 30 hours and is reported on a numerical scale of 0-100, 100

TABLE 11 [Rotating cylinder testl Physiml fli fi 1mm Physical Properties After Test Sample No. P t

81' can f Y'fi g ig v. I. f Y-fi 5 1 Na gall N. N.

111.0 13.03 101.3 14. 1s .01 1.2 218. 1 21. 32 117 896. 0 54. 40 O9 3. 5 218.6 22.20 120 112.0 52m 1 .01 4.0 98.3 12. 52 122 333.0 21.11 .01 3.2 111.8 13.30 118 430.0 3201 .04 3.1 110. 3 13. 47 121 317. 8 26. 51. 07 4. 5 13a. 3 11.44 122 498.0 31.12 .04 3. 3 121.3 14.88 120 1132.0 03.30 4.2 101.1 18.1 110 m0 40.31 3. 2 153. 2 17. 18 121 312. 0 2,. 21 I 3. 0

65 representing a perfectly clean piston. The following table gives the results of these tests.

TABLE rvf 10 K. V. at 210 F. P v m Hours N N mm crease in Rs No. Before After Viscosity as Test Test v 11 30 7. 1 18. 11 3a 78 a1. 2

A series of laboratory stability-corrosion tests were also conducted. In these tests, a 160 cc. sample of the composition to be tested is placed in a 19 x 1%" test tube. Ferric-2-ethylhexoate is blended with the oil in an amount of 0.012%. calculated as E6203, and 0.1% of 200mesh PbBlz is added at the start of the test. 70 liters of air per hour are blown through the oil at 280 F. by means of a bubbler device over which a hollow steel cylinder is placed so that it forms an air lift. The oil is thus Dumped up through the cylinder. A polished section of a copper-lead bearing with an area of 5.7 cm} is held at the inside top portion of the steel cylinder by 1 /2" of No. 22 copper wire. Asthe oil is pumped up through the cylinder, it flows past this copperlead bearing and back down the outside of the cylinder to the bottom of the tube. In this way a constant circulation of oil is maintained. Changes in the characteristics of the oil, the loss in weight of the bearings, the sludge deposit in the tube and the lacquer deposit on the cylinder are noted. The following table gives 25 the results of several of these tests.

The reaction product used in these tests was prepared by treating oleone with a pelleted silicaalumina catalyst at 650 F. for a period of 5 hours in an autoclave. The product obtained had the following properties.

The corrosion inhibitor used is obtained by reacting 100 parts of pinene and 90 parts of S. A. E. motor oil with 40.8 parts of phosphorus pentasulfide at about 150 C.

10 added to the product oi Example IV and the efiect on the pour point was noted. This pour depressant consisted essentially of tetrawax phenol phthalate.

g A. S. T. M.

Composition: pour point Product of Example IV +10 F. Product of Example IV +0.25% pour depressant 10 1" 10 Product or Example IV +0.125%

pour depressant 5 F.

may, by the process of this invention, be converted into products that are useful. Oleone is used, however, because it is readily available and furnishes a good example. Other similar unsaturated ketones containing either similar or mixed alkene radicals, each having from between ten and thirty carbon atoms, can also be used as the starting material.

What is claimed is: 1

1. The product formed by treating an urisaturated ketone having ten to thirty carbon atoms in each alkene radical with a catalyst selected from the group consisting of synthetic silica-alumina cracking catalyst and activated montmorillonite clay, at a temperature falling within the range varying between about 500 F.

and about 650 F. and for a period of time varying between about three hours and about seven hours.

2. The product formed by treating oleone with a catalyst selected from the group consisting of synthetic silica-alumina cracking catalyst and montmorillonite clay, ata temperature falling In order to test the effectiveness of pour de- TABLE V [Laboratory stability-corrosion test] Ou-Ib Per Cent K. V. at Bearin Stri 8111 net 210 F. Wt. p in will; m

. gms.

' a 12% it 122; is v M011 Product y a 1.9 14 7 53.1

3% 3.: 1%; car .0504 Nil Nil Reaction Product plus oi 16 no a. 4

Corrosion In it I 2 0 7 11 M n 40 0.4 12.42 42.6 .0004 Nil Nil x within the range varying between about 500 1''.

and about 650 F. and for a period oi time varying between about three hours and about seven pressants on the. new compositions, various perhours.

centages of a commercial pour depressant were FERDINAND P. O'I'lO.

REFERENCES crrnn The following rei'erarcesare or recordin the ills oi this patent:

UNITED STATES PATHITB- Number Name Date

OTHER REFERENCES Karrer: 0mm Chemistry, page 1500038).

-Pub.Co.,NewYork.

Taylor: Richterorganie Grammar! 137-0 (WhNordemanaPub-Omilew! 

